JPS6289877A - chemical copper plating liquid - Google Patents
chemical copper plating liquidInfo
- Publication number
- JPS6289877A JPS6289877A JP23017585A JP23017585A JPS6289877A JP S6289877 A JPS6289877 A JP S6289877A JP 23017585 A JP23017585 A JP 23017585A JP 23017585 A JP23017585 A JP 23017585A JP S6289877 A JPS6289877 A JP S6289877A
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- copper plating
- copper
- complexing agent
- chemical copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は優れた物性を有する銅めっき被膜を、高速度で
析出させることを可能にする化学銅めっき液に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a chemical copper plating solution that makes it possible to deposit a copper plating film having excellent physical properties at a high rate.
本発明は化学銅めっき液において、第二銅イスーンの錯
化剤としてヒドロキシエチルエチレンジアミン三酢酸及
びそのナトリウム塩のうち少なくとも一種と、第１銅イ
オンの錯化剤として脂肪族アミノ酸類のうち少なくとも
１種と、第１回イオンの錯化剤としてジビリジルとその
誘導体、７エナンスロリンとその誘導体、シアン化合物
、ジアミン類のうち少なくとも１種と、非イオン系界面
活性剤を添加することにより、優れた物性の銅めっき被
膜を高速度で析出させることを可１１目にしたものであ
る。The present invention provides a chemical copper plating solution in which at least one of hydroxyethylethylenediaminetriacetic acid and its sodium salt is used as a complexing agent for cupric ions, and at least one of aliphatic amino acids is used as a complexing agent for cuprous ions. By adding at least one of diviridyl and its derivatives, 7-enanthroline and its derivatives, cyanide compounds, and diamines as a complexing agent for the first ion, and a nonionic surfactant, excellent physical properties can be achieved. It is possible to deposit a copper plating film at a high speed.
一般に、自己触媒反応を利用して無電気的に銅めっき被
膜を析出させることを特徴とする特許めっき液は、銅イ
オン供給源と、銅イオン錯化剤と、銅イオンを金属銅に
還元する還元剤と、ＰＨ調整剤とから成っている。しか
し、これは非常に分解しやすく、得られる銅めっき被膜
は脆く機械的特性が不十分であった。そこでめっき液の
自己分１’７ｆを防止し、かつめっき被膜の機械的特性
を向上させるため、様々な添加剤が考案されてきた。In general, a patented plating solution that is characterized by electrolessly depositing a copper plating film using an autocatalytic reaction includes a copper ion supply source, a copper ion complexing agent, and a method that reduces copper ions to metallic copper. It consists of a reducing agent and a pH adjusting agent. However, this was very easy to decompose, and the resulting copper plating film was brittle and had insufficient mechanical properties. Therefore, various additives have been devised in order to prevent the self-containing 1'7f of the plating solution and to improve the mechanical properties of the plating film.
例えば特開昭５１−１０５９５２号公報にはめっき被膜
の機械的特性のうち伸び特性を著しく改善する添加剤と
して、２．２’−ジビリジルとポリエチレングリコール
が上げられている。For example, JP-A-51-105952 lists 2,2'-dipyridyl and polyethylene glycol as additives that significantly improve the elongation properties among the mechanical properties of the plated film.
〔発明が解決しようとする問題点及び目的〕しかし、前
記の従来技術の例では、伸び特性の優れた銅被膜を析出
させる速度が５〜４μ”し省 と遅いため、例えばアデ
ィティブ法によるプリント回路板製造法にこの技術を応
用した場合、めっき時間が非常に長くなるという問題点
があった。[Problems and objects to be solved by the invention] However, in the example of the prior art described above, the rate of depositing a copper film with excellent elongation properties is as slow as 5 to 4 μ''. When this technology was applied to a plate manufacturing method, there was a problem in that the plating time was extremely long.
そこで本発明では、従来のこの様な問題点を解決するた
め、優れた物性を有する銅めりき被膜を、高速度で析出
させることを可能にする化学銅めっき液を提供すること
を目的とする。Therefore, in order to solve these conventional problems, the present invention aims to provide a chemical copper plating solution that makes it possible to deposit a copper plating film having excellent physical properties at a high speed. .
〔問題点を解決するための手段〕
本発明の化学銅めっき液は、銅イオン、銅イオンの錯化
剤、銅イオンの還元剤、及びＰＨ調整剤より成る化学銅
めっき液において、（ａ）第二銅イオンの錯化剤として
、ヒドロキシエチルエチレンジアミン三酢酸及びそのナ
トリウム塩のうち少なくとも一種と、（ｂ）第一銅イオ
ンの錯化剤として脂肪族アミノ酸類のうち少なくとも一
種と、（ｃ）第一銅イオンの錯化剤としてジビリジルと
その誘導体、シアン化合物、ジアミン類のうち少なくと
も一種と、（ｄ）非イオン系界面活性剤を添加すること
を特徴とする。[Means for Solving the Problems] The chemical copper plating solution of the present invention is a chemical copper plating solution consisting of copper ions, a complexing agent for copper ions, a reducing agent for copper ions, and a PH adjuster, which includes (a) (b) at least one kind of aliphatic amino acids as a complexing agent for cuprous ions; (c) at least one kind of aliphatic amino acids as a complexing agent for cuprous ions; It is characterized in that at least one of diviridyl and its derivatives, cyanide compounds, and diamines is added as a complexing agent for cuprous ions, and (d) a nonionic surfactant.
本発明の化学銅めっき液の第二銅イオンの錯化剤である
とドロキシエチルエチレンジアミン＝酢酸及びそのナト
リウム塩は１０〜ｓ ｏ ’／ｌ、更には２５〜ａ ｓ
９７ｔの濃度範囲が好ましい。その理由は１０ ’／
ｌより少ないとめつき液の安定性が悪くなり、また５
０ ’／ｌより多いと速度効果が得られないと同時に非
経済的である。第一銅イオンの錯化剤である脂肪族アミ
ノ酸類は例えば、アミノ錯酸、α−アミノプロピオン酸
等より少なくとも一種選択され、その添加量は１〜５０
’／を更には３〜２０ ’／ｌの範囲が好ましい。そ
の理由は１４より少ないとめっき液の長寿命化効果及び
被膜の引張り強度に対する改善効果が得られず、５０’
／。As a complexing agent for cupric ions in the chemical copper plating solution of the present invention, droxyethylethylenediamine=acetic acid and its sodium salt have a concentration of 10 to s o'/l, more preferably 25 to a s
A concentration range of 97t is preferred. The reason is 10'/
If the amount is less than 1, the stability of the plating liquid will deteriorate, and
If the amount is more than 0'/l, no speed effect can be obtained and at the same time it is uneconomical. At least one aliphatic amino acid as a complexing agent for cuprous ions is selected from amino complex acids, α-aminopropionic acid, etc., and the amount added is 1 to 50%.
'/l is preferably in the range of 3 to 20'/l. The reason for this is that if the number is less than 14, the effect of extending the life of the plating solution and the effect of improving the tensile strength of the coating cannot be obtained;
/.
より多いとめっき速度は著しく低下するためである。This is because if the amount is larger, the plating speed will drop significantly.
また第一銅イオンの錯化剤であるジビリジルとその誘導
体、シアン化合物、ジアミン類のうち少なくと一種は、
２．２′−ジビリジル、 ２ 、２’ビキノリン、１．
１０−７エナンスロリン、シアン化ナトリウム、シアン
化カリウム、シアン化金カリウム、７エロシアン化カリ
ウム、エチレンジアミン等より少なくとも一種選択され
、その添加ｉａ ハ［１１〜１００１ｒ′／１ 更ＧＣ
ハｉ 〜５０ ”／１ ）範［１１１が好ましい。その
理由はＱ、１）ｊより少ないと得られる被膜の伸び特性
が劣下し、１００ ”／ｌより多いとめつき速度を著し
く低下させるためである更に、非イオン系界面活性剤は
ポリエチレングリコール、ポリプロピレングリコール、
ポリエチレングリコールステアリルアミン、ポリエチレ
ングリコールジメチルエーテル等より少なくとも一種選
択することができ、その添加量は０．１〜１００ケｔが
よい。その理由はａ、 ’＋ ’／ｌより少ないと十分
な柔軟性、伸び特性が得られず、ｉ ｏ ｏ ／ｌよ
り多いとめっき速度の低下をまねき、また著しく発泡す
るため好ましくない。In addition, at least one of diviridyl and its derivatives, cyanide compounds, and diamines, which are complexing agents for cuprous ions,
2.2'-diviridyl, 2,2'biquinoline, 1.
At least one selected from 10-7 enanthroline, sodium cyanide, potassium cyanide, potassium gold cyanide, potassium 7-erocyanide, ethylenediamine, etc., and its addition ia [11-1001r'/1 Further GC
The range [111 is preferable.The reason is that if it is less than Q, 1) j, the elongation properties of the obtained film will deteriorate, and if it is more than 100"/l, the plating speed will be significantly reduced. In addition, nonionic surfactants include polyethylene glycol, polypropylene glycol,
At least one type can be selected from polyethylene glycol stearylamine, polyethylene glycol dimethyl ether, etc., and the amount added is preferably 0.1 to 100 kets. The reason for this is that if it is less than a, '+'/l, sufficient flexibility and elongation properties cannot be obtained, and if it is more than i o o /l, the plating rate will decrease and foaming will occur, which is not preferable.
本発明の前記（ａ）〜（ｄ）の錯化剤及び添加剤は４種
同時に使用することによりはじめて本発明の目的を達成
することができる。また本発明の化学銅めっき液の基本
成分である８４イオンは硫酸銅により供給するのが一般
的であるが、その他に水酸化鋼、ギ酸銅、硝酸銅、金属
鋼等がある。また銅イオンの還元剤としてホルマリン、
シアリンｍｈｐｕ調整剤として水酸化す） ＩＪウム、
水酸化カリウムを用いることができる。本めっき液を操
作する条件は、温度が５０〜９０℃更には６５〜７５℃
の範囲、ＰＨは１１．０〜１五〇更には１１．５〜１２
．５の範囲が好ましく、これらの条件の範囲内であれば
、本めっき液の特徴を十分に発揮することができる。The object of the present invention can only be achieved by using four complexing agents and additives (a) to (d) at the same time. The 84 ion, which is a basic component of the chemical copper plating solution of the present invention, is generally supplied by copper sulfate, but other sources include hydroxide steel, copper formate, copper nitrate, and metallic steel. In addition, formalin is used as a reducing agent for copper ions.
sialin hydroxide as a mhpu regulator) IJum,
Potassium hydroxide can be used. The conditions for operating this plating solution are that the temperature is 50 to 90℃ and further 65 to 75℃.
range, PH is 11.0-150 and even 11.5-12
．． The range of 5 is preferable, and within the range of these conditions, the characteristics of the present plating solution can be fully exhibited.
本発明を実施例により更に詳しく説明する。第１表に本
発明部用いた化学銅めっき液の組成及びめっき速度、得
られた被膜の物性を示した。（実施例１〜８）また第２
表には比較例として用いためっき液の組成及びめっき速
度、得られた被膜の物性を示した。（比較例１〜２）め
っき液の容量は２ｔで、液温は７０±１°Ｃ５ＰＨは１
２．４±ａ、１とし、常時空気攪拌を行い約３０μｍの
銅被膜を析出させるのに要した時間によりめっき速度を
算出した。また被膜の機械的特性は引張り試験で評価し
、サンプルとして、所定の前処理を施こした電解鋼箔を
第１．２表のめつき液中に浸漬して得られた化学銅めっ
き被膜を剥離し、１０ｍ＋Ｘ７０叫の形状に切１ｔ７ｉ
Ｌ、たちのを用いた。The present invention will be explained in more detail with reference to Examples. Table 1 shows the composition of the chemical copper plating solution used in the present invention, the plating rate, and the physical properties of the resulting coating. (Examples 1 to 8) Also, the second
The table shows the composition of the plating solution used as a comparative example, the plating speed, and the physical properties of the obtained film. (Comparative Examples 1-2) The capacity of the plating solution was 2 tons, the solution temperature was 70±1°C, 5PH was 1
The plating rate was calculated from the time required to deposit a copper film of about 30 μm with constant air stirring. In addition, the mechanical properties of the coating were evaluated by a tensile test, and a chemical copper plating coating obtained by immersing electrolytic steel foil that had been subjected to a specified pretreatment in the plating solution shown in Table 1.2 was used as a sample. Peel it and cut it into a shape of 10m+X70mm
L, Tachino was used.
第１．２表より明らかなように、従来の化学ｌｌイめつ
き液のめつき速度２〜３μｍ％ｈ に対して本発明の
化学銅めっき液のめつき速度は４〜６μｒｒＶ／ｈであ
り、２〜６倍の高速化が達せられる。しかも得られるめ
っき被膜の物性のうち抗張力に優れていることがわかる
。As is clear from Table 1.2, the plating speed of the chemical copper plating solution of the present invention is 4 to 6 μrrV/h, whereas the plating speed of the conventional chemical plating solution is 2 to 3 μm%h. , a speedup of 2 to 6 times can be achieved. Furthermore, it can be seen that among the physical properties of the resulting plating film, tensile strength is excellent.
以上述べた様に本発明の化学銅めっき液により機械的特
性の優れた銅被膜を高速度で析出させることができる。As described above, a copper coating with excellent mechanical properties can be deposited at high speed using the chemical copper plating solution of the present invention.
従って本発明の化学銅めっき液を例えば、プリント回路
板の製法の１つであるアディティブ法に用いれば、優れ
た信頼性を有する回路板を短時間に製造することができ
る。Therefore, if the chemical copper plating solution of the present invention is used, for example, in the additive method, which is one of the methods for manufacturing printed circuit boards, circuit boards with excellent reliability can be manufactured in a short time.
以 上that's all
Claims (1)
調整剤を含む化学銅めっき液において、（ａ）第二銅イ
オンの錯化剤としてヒドロキシエチルエチレンジアミン
三酢酸及びそのナトリウム塩のうち少なくとも一種と、
（ｂ）第一銅イオンの錯化剤として脂肪族アミノ酸類の
うち少なくとも一種と、（ｃ）第一銅イオンの錯化剤と
してジビリジルとその誘導体、フエナンスロリンとその
誘導体、シアン化合物、ジアミン類のうち少なくとも一
種と、（ｄ）非イオン系界面活性剤を添加することを特
徴とする化学銅めっき液。Copper ion, copper ion complexing agent, copper ion reducing agent, PH
In a chemical copper plating solution containing a regulator, (a) at least one of hydroxyethylethylenediaminetriacetic acid and its sodium salt as a complexing agent for cupric ions;
(b) at least one aliphatic amino acid as a complexing agent for cuprous ions, and (c) diviridyl and its derivatives, phenanthroline and its derivatives, cyanide compounds, and diamines as a complexing agent for cuprous ions. A chemical copper plating solution containing at least one of the above and (d) a nonionic surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23017585A JPS6289877A (en) | 1985-10-16 | 1985-10-16 | chemical copper plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23017585A JPS6289877A (en) | 1985-10-16 | 1985-10-16 | chemical copper plating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6289877A true JPS6289877A (en) | 1987-04-24 |
Family
ID=16903779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23017585A Pending JPS6289877A (en) | 1985-10-16 | 1985-10-16 | chemical copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6289877A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378407A1 (en) * | 1989-01-13 | 1990-07-18 | Hitachi Chemical Co., Ltd. | Electroless copper plating solution |
| JPH02250978A (en) * | 1989-03-23 | 1990-10-08 | Matsushita Electric Ind Co Ltd | Electroless copper plating solution |
-
1985
- 1985-10-16 JP JP23017585A patent/JPS6289877A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378407A1 (en) * | 1989-01-13 | 1990-07-18 | Hitachi Chemical Co., Ltd. | Electroless copper plating solution |
| US5076840A (en) * | 1989-01-13 | 1991-12-31 | Hitachi Chemical Co. Ltd. | Electroless copper plating solution |
| JPH02250978A (en) * | 1989-03-23 | 1990-10-08 | Matsushita Electric Ind Co Ltd | Electroless copper plating solution |
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